Primary disazo dyes derived from diamino carbazoles and arylimino compounds



Patented Jan. 1, 1929.

UNITED STATES 'ATENT OFFICE.

HEINRICH CLINGESTEIN, or 'COLOGNE-ON-THE-RHINE, GERMANY, AND HARRY w.

GRIMMEL, on ALBANY, NEW YORK, ASSIGNORS r0 GRASSELLI nrns'rnnr con-IORATION, or NEW YORK, N. Y., A conPonArIoN or DELAWARE.

PRIMARY DISAZO DYES DERIVED FRQM DIAMINO CARBAZOLES AND ARYIIIMINO VCOMPOUNDS. 7

No Drawing. Original application filedMarch 21, 1927, Serial No.177,208, and in Germany March 24,

1926. Divided and this application filed November 28, 1927. Serial No.236,361.

The present invention. relates to new primary disazo ldyes derived fromdiamino'carbazoles and arylimino compounds.

WVe have found that exceedingly valuable new azo-dye'stufls, insolublein water, having most probably the general formula:

wherein It represents the residue of an unsulfonated diamino-carbazolecompound, and it, represents an unsulfonated 'aryl-iminocompound, areobtained by coupling the tetrazo-coinpounds of unsulfonateddiamino-carbazole compounds with unsulfonated arylimino-coniipounds suchas, for example, arylids of 2.3-hydroxy-naphtholic acid,hydroxynaphtho-carbazoles, diaceto-acetic acid arylids or the like.

The new dyestuffs thus obtained are, in the dry state, yellowish-brownto violet to blue to black powders, insoluble in water, soluble inconcentrated sulfuric acid to the production of solutions which, for themost part, have a bluish coloration. \Vhen produced directly onvegetable fibers, these dyestuffs dye very clear yellowish-brown toviolet to blue to deep black shades of particular fastness properties;for example, fastness to light and to hier-boiling. These fastnessproperties especially distinguish our dyestuffs from the dyestuffsobtained by coupling tetrazotized diamino-carbazole-compounds withB-naphthol, which latter dyestuffs already are known.

The most valuable of our dyestuffs are those with deep blue to blackshades.

Our dyestuifs produce excellent lakes when mixed with, or precipitatedupon, the usual substrates.

In order to further illustrate the invention, the following example isgiven, it being understood that our invention is not limited thereto:

Example.

The yarn is well boiled and dried and then padded with a solutioncontaining per liter 12 grams of 7-hydroxy-naphtho-carbazole, 25 cone.of 34 B. caustic sodasolution and 20 com. of Turkey red oil. Afterdeveloping with a solution containing; per liter the tetrazo-compoundfrom 5 grams of 2.7-diaminocarbazole, the yarn is found to be dyed deepblack of exceedingly good fastness properties.

The dyestuif, precipitated on the fibre has most probably the formula:

The dyestuff itself is a bluish-black powder insoluble in water butsoluble in concentrated sulfuric acid with a blue coloration. By mixingthe sulfuric acid solution with water, reddish-blue flakes are obtained.In pyridine it dissolves with a bluish coloration. By reduction withstannous chloride and hydrochloric acid there are obtained2.7-diamino-carbazole and 8-amino-7-hydroxy-2-1-naphtho-carbazole havingthe formula:

wherein R represents the residue of an unsulfonated dianiino carbazo-lecompound and R represents the residue of an unsulfonatedhydroxy-naphtho-carbaz0le compound which dyestuffs are, in thedry-state, yellowishbrown to =vi0let 'to blue to black powders,insoluble in Water, and soluble in concentrated sulfuric acid to theproduction of solutions Which, forthe most partfhavea bluishcoloration.

4. As new products Water-insoluble azo dyestuffs having the generalformula:

sulfuric acid to the ;production of solutions- Which, for the mostipart,have a. bluish. coloration.

5. As a new product, a Water-insoluble azodyestufl' having most probablythe formula:

being -in the dry state a ibluishebleck powder insoluble in Water butsoluble in concentrated sulfuric acid with a blue coloration.

=6. lDhQIl'lElillGI'lYlllKlYGCl witlnthe dyestufi dei'finedin-claim 3.

7. The material dyed with the dyestuif defined inclaim 4.

8. The material dyed With ithe dyestufi" defined in claim'5.

in testimony whereof We have hereunto set our hands.

HEINRICH -CLINGEST-EIN. HARRY GRIMMEL.

